Alkyl-substituted cyclohexenes



United States Patent Office 3,405,188 Patented Oct. 8, 1968 3,405,188 ALKYL-SUBSTITUTED CYCLOHEXENES Herman S. Bloch, Skokie, Ill., assignor to Universal Oil Products Company, Des Plaines, ]ll., a corporation of Delaware No Drawing. Original application Oct. 28, 1964, Ser. No. 407,233. Divided and this application June 30, 1967, Ser. No. 650,186

4 Claims. (Cl. 260-666) ABSTRACT OF THE DISCLOSURE A monoolefin having from about 9 to about carbon atoms is condensed with a conjugated diene to produce an alkyl substituted cyclohexene suitable for use in the manufacture of detergents.

This application is a division of my copending application Ser. No. 407,233, filed Oct. 28, 1964, now abancloned.

This invention relates to a novel biodegradable detergent and to a process for making the same. More specifically, this invention relates to a novel detergent whose composition is:

wherein R is an alkyl group of substantially normal character having from 1 to about 17 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl group of substantially normal character having from 1 to about 17 carbon atoms such that the sum of carbon atoms in R plus R does not exceed 18, R" is selected from the group consisting of hydrogen and methyl and X is a hydrophilic group. Further, this invention relates to a process for the production of the above described novel detergent which comprises condensing a monoolefin having from about 9 to about 20 carbon atoms with a conjugated diene and introducing a hydrophilic group into the condensed product. The resulting product which contains both a hydrophilic and a hydrophobic group is a detergent material subject to bacterial attack and degradation in a subsequent sewage treatment process after the detergent has been used in a laundering or other cleaning operation and discharged into such sewage treatment facilities.

One of the major problems prevalent in centers of population throughout the world is the disposal of sewage and the inactivation of detergents dissolved in the sewage in even small quantities. Such disposal problem is especially vexacious in the case of those detergents having an alkylaryl structure as the nuclear portion of the detergent molecule. These detergents produce stable foams in hard or soft waters in such large quantities that the foam clogs sewage treatment facilities and often appears in sufficient concentration in such facilities to destroy the bacteria necessary for sufficient biological action for proper sewage treatment. One of the principal offenders of this type of detergent is the alkylaryl sulfonates, which, unlike the fatty acid soaps, do not precipitate when mixed with hard water containing calcium or magnesium ions in'solution. Since these compounds are only partly biodegradable, the detergent persists in solution and is carried through the sewage treatment plant in substantially unchanged or still active form. Having an abiding tendency to foam, especially when mixed with aerating devices and stirrers, large quantities of foam are discharged from the sewage digestion plant into rivers and streams where the continuing presence of the detergent is marked by large billows of foam on the surface. Other offenders of this type of detergent are the polyoxyalkylated alkylphenols and the polyoxyalkylated alkylanilines. These same synthetic detergents also interfere with the anaerobic process of degradation of other materials such as grease, and this compounds further the pollution caused by sewage plant efiluents containing such detergents. These dilute detergent solutions often enter subsurface water currents which feed into underground water strata from which many cities draw their water supplies and these detergents find their way into the water supplies drawn from water taps in homes, hospitals and schools. Occasionally these detergents turn up in sufficient quantities in tap water to make drinking water foam as it pours from the tap.

It is an object of this invention to produce a detergent capable of biological degradation during the treatment of sewage containing such detergents. It is another object of this invention to provide a process for making the biodegradable detergent. It is a more specific object of this invention to produce a detergent of the composition:

wherein R, R, R" and X are as described hereinbefore. It is another more specific object of this invention to produce the biodegradable detergent by condensing a monoolefin with a conjugated diene and introducing a hydrophilic group into the condensed product.

One of the starting materials in the process of this invention is a monoolefin, preferably of substantially normal character having about 9 to 20 carbon atoms per molecule. This material may be prepared by any well known method such as wax cracking or it may be prepared from substantially normal paraffins. In this latter source the normal paratfins are separated from hydrocarbon mixtures by molecular sieve extraction. The normal paraffin may be reacted with a halogen selected from the group consisting of chlorine and bromine to form the alkyl halide. The alkyl halide is then dehydrohalogenated to form the substantially normal monoolefin.

Another of the starting materials in the process of this invention is a conjugated diene. This material is preferably selected from the group consisting of 1,3-butadiene and piperylene.

The heart of this invention lies in the reaction of the monoolefin with the conjugated diene. This reaction is carried out by thermally condensing the monoolefin with the conjugated diene at temperatures of from about C. to about 250 C. and pressures of atmospheric or moderately superatmospheric. The thermally condensed product, which is a substituted cyclohexene, is separated and is thereupon converted to a water soluble surface active detergent by introducing a hydrophilic group into it. The thermal condensation reaction is further illustrated by the reaction of 4-nonene with 1,3-butadiene to form 4-propyl-5-butyl cyclohexene.

The resulting substituted cyclohexene may be treated 3 in a number of conventional ways to introduce hydrophilic group into its structure thereby forming a detergent. For example, the hydrophilic group may be a sulfate groups, a sulfonate group or a polyoxyalkylene group.

The sulfate group may be introduced by reacting the substituted cyclohexene with concentrated sulfuric acid at temperatures below 50 C., and preferably about C. to C. The resulting sulfate is then neutralized with a basic material, preferably a metal hydroxide or am monia to form the finished surface active product. The alkali metals are preferably cations for said. metal hydroxide, sodium and potassium being especially preferable.

The sulfonate group may be introduced into the substituted cyclohexene by hydrohalogenating said cyclohexene and reacting the resulting cyclohexylhalide with a metal sulfite salt thereby forming the sulfonate. The halogen is preferably selected from the group consisting of chlorine and bromine while the metal sulfite is preferably selected from the group consisting of sodium sulfite and potassium sulfite. Alternatively, the sulfonate .may be formed by reacting the cyclohexene with a metal bisulfite at temperatures of about 100 to 125 C. The metal bisulfite is preferably selected from the group consisting of sodium bisulfite and potassium bisulfite.

Another procedure for introducing hydrophilic groups into the substituted cyclohexene is to hydrate the cyclohexene with dilute acid such as hydrochloric acid, hydrofluoric acid or sulfuric acid or with aqueous boron fluoride. The resulting cyclohexanol may be thereupon sulfated or oxyethylated to render it water soluble and surface active. This latter step is accomplished by reacting the cyclohexanol with ethylene oxide in the presence of a trace amount of basic material such as sodium acetate, sodium carbonate or sodium hydroxide at temperatures of about 80 C. to form the hydrophilic polyoxyalkylene group.

These and other Well known methods and hydrophilic groups may be employed to form a water soluble surface active biodegradable detergent from the substituted cyclohexene. The resulting detergent has the following generic composition:

wherein R is an alkyl group of substantially normal character having from about 1 to about 17 carbon atoms, R is selected from the group consisting of hydrogen and an alkyl group of substantially normal character having from 1 to about 17 carbon atoms such that the sum of carbon atoms in R plus R does not exceed 18, R is selected from the group consisting of hydrogen and methyl and X is a hydrophilic group preferably selected from the group consisting of a sulfate (X is OSO M where M is hydrogen, amine ion or an equivalent of a metal), a sulfonate (X is SO M Where M is as defined above) and a hydroxypolyoxyalkylene [X is --O(C,,H ,O) I-I where n is 2 or 3 and y is a number from 5 to 30].

It is to be noted that when the cyclohexene is formed from butadiene and the monoolefin, R is hydrogen whereas R" is a methyl group when piperylene is used as the conjugated diene. The relative number of carbon atoms in R and R is determined by the position of the double bond in the monoolefin. Thus when the monoolefin is an alpha olefin, then R will be hydrogen and R will contain all the carbon atoms in the original monoolefin except the two which become part of the cyclic structure.

The resulting detergents are readily degraded by treatment in conventional sewage facilities.

The following examples are presented to illustrate the process of this invention but it is not intended to limit the scope of this invention to the feed materials or products of those specifically shown reactions the examples.

EXAMPLE I A glass liner containing 189 grams (1.5 mole) of 4- nonene and cc. hexane is sealed into an autoclave and about 27.0 grams of 1,3-butadiene is pressured in. The autoclave and contents are heated to a temperature of 150 C. for a period of about 8 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired 4-propyl-5-butyl cyclohexene is separated by ordinary batch fractionation. The substituted cyclohexene is introduced into a flask which is immersed in a bath maintained at 0 C. Concentrated sulfuric acid at a temperature of 0 C. is introduced into the flask and the' contents thoroughly mixed. The resulting solution is neutralized in a cooling bath with a sodium hydroxide solution until a pH of 7 is attained. The product is dried and extracted with ethanol to separate sodium sulfate from the organic sulfate. The latter is a crystalline cream colored solid which is completely soluble in Water, foams and shows good wetting and other surface-active properties.

Example II A mixture of about 252 grams (1.5 mole) of 10- methyI-B-undecene and 100 cc. of hexane is introduced into a glass liner and sealed into an autoclave whereupon about 34.1 grams of 1,3-pentadiene (piperylene) is added. The autoclave and contents are heated to about 175 C. and maintained at this temperature for a period of about 12 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired 3-methyl-4-(6-methyl heptyl)-5-ethyl cyclohexene is separated by ordinary batch fractionation. The substituted cyclohexene is hydrated with 80% sulfuric acid and subsequent dilution at 25 C. to form the corresponding cyclohexanol, which is separated and placed in a glass liner and sealed into an autoclave after addition of 0.5% of powdered sodium hydroxide. Sufficient ethylene oxide is pressured in to result in a ratio of 9 moles of ethylene oxide to 1 mole of cyclohexanol. The autoclave and contents are heated to C. and maintained at that temperature for a period of 2 hours at the end of which time the autoclave and the contents thereof are cooled to room temperature and the desired polyoxyethylated detergent is removed.

Example III A glass liner containing about 252 grams (1.5 mole) of dodecene-l and 200 cc. of hexane is sealed into an autoclave and about 27.0 grams of 1,3-butadiene is pressured in. The autoclave and contents are heated to a temperature of about C. and maintained at this temperature for a period of about 16 hours at the end of which time the autoclave and contents thereof are cooled to room temperature and the desired 4-decyl cyclohexene is separated by ordinary batch fractionation. The substituted cyclohexene is converted to the corresponding cyclohexyl halide by reaction with anhydrous hydrogen chloride, and the product is contacted with a slight molar excess of concentrated sodium sulfite by mixing together in a glass flask. The mixture is maintained at 115 C. for one hour whereupon the desired sulfonate is recovered from the flask.

I claim:

1. A process for the production of an alkyl substituted cyclohexene suitable for use in the manufacture of detergents by thermally and noncatalytically condensing reactable proportions of a monoolefinic acyclic hydrocarbon having from about 9' to about 20 carbon atoms with a member of the group consisting of butadiene or piperylene at a temperature of from about 150 C. to about 250 C.

2. The process of claim 1 further characterized in that said monoolefinic hydrocarbon is 4-nonene.

3. The process of claim 1 further characterized in that said monoolefinic hydrocarbon is I'O-methyI-B-undecene.

References Cited UNITED STATES PATENTS 2,336,208 12/1943 Alder 260666 2,662,102 12/ 1953 Whitman 260-666 3,244,678 4/ 1966 T ocher 26 0-666 3,344,204 9/1967 Clough 260-666 DELBERT E, GANTZ, Primary Examiner.

4. The process of claim 1 further characterized in 10 V. OKEEFE, Assistant Examiner.

that said monoolefinic hydrocarbon is dodecene-l. 

